TEXTILE PRODUCT TREATMENT

Abstract: A textile product treatment comprising a graft fluorocopolymer composed a polymer of a fluoromonomer as the backbone and a polymer, as the graft, of a fluorine-free macromonomer copolymerizable with the fluoromonomer and having an addition-polymerizable unsaturation at its terminal. The treatment has excellent water-and oil-repellency and capability of antistaining finishing.

Description: Field of the Invention The present invention relates to an agent for treating a textile, particularly relates to a textile treatment agent comprising a fluorine-containing graft polymer. Related Art Hitherto, known is a water- and oil-repellent comprising a random copolymer of a polyfluoroalkyl group-containing monomer and another copolymerizable hydrocarbon monomer. For example, a copolymer of the polyfluoroalkyl group-containing monomer and a long chain alkyl group-containing (meth)acrylate such as stearyl (meth)acrylate can have better water- and oil-repellency and better resistance to the washing and dry cleaning than a homopolymer of the polyfluoroalkyl group-containing monomer (cf. Japanese Patent Kokai Publication Nos. 9619/1980 and 29501/1980 and Japanese Patent Kokoku Publication Nos. 8068/1985 and 56912/1988). Recently filed was a patent application disclosing that a graft copolymer in which a branch segment made of a fluoropolymer is grafted to a backbone segment made of a hydrocarbon polymer can cover more effectively a treated substrate such as a fiber than the above random copolymer and can give the high water- and oil-repellency even in a small amount (cf. Japanese Patent Kokoku Publication Nos. 50082/1986, 21715/1988, 43509/1988 and 67511/1988). On the other hand, hitherto, a random copolymer of a polyfluoroalkyl group-containing monomer and a copolymerizable specific monomer is well-known as the agent for giving the stainproof property to a textile typically such as a carpet. For example, Japanese Patent Kokai Publication Nos. 642/1971 and 35188/1977 can be referred to. It is reported that a mixture of a polyfluoroalkyl group-containing compound and a water-insoluble addition-polymerization polymer having a specific transition temperature can be used for the stainproof treatment of carpet. Japanese Patent Kokai Publication Nos. 7600/1972 and 128075/1980 can be referred to. However, the above conventional random copolymer, graft copolymer and mixture still have insufficient water- and oil-repellency and stainproof property, and the treated fiber lacks in softness. When these copolymers prepared by the solution polymerization are used at a low temperature, the solubility is insufficient so as to give problems such as solidification in solution. Accordingly, there is a problem that the composition of the used copolymer and the kind of solvent are limited. Generally, in the case of the random copolymer, the fluorine-containing component and the hydrocarbon component are present only as monomeric units so that the functions thereof are cancelled out. In the case of the graft copolymer, a microscopic phase separation structure is formed and the functions of both of the fluorine-containing component and the hydrocarbon component can be theoretically exhibited. However, the above Patent Publications suffer from the disadvantages that the graft copolymer isation has an insufficient graft efficiency and a homopolymer is present, or the number and length of the branches are not uniform, and that the functions of the graft copolymer are not sufficiently exhibited. SUMMARY OF THE INVENTION An object of the present invention is to provide a textile treatment agent having excellent water- and oil-repellency and stainproof property. The present inventors intensively studied to solve the above problems. Finally, the present inventors found that the object is achieved by the use of a graft fluorocopolymer having a backbone of a polymer of a fluoromonomer and a branch of a polymer of a macromonomer, the graft fluorocopolymer being prepared by copolymerizing the fluoromonomer with the macromonomer which is a fluorine-free macromonomer having an addition-polymerizable unsaturated group at a molecular end. Accordingly, the gist of the present invention resides in a textile treatment agent which comprises the graft fluorocopolymer prepared by the above method as an active component. The textile treatment agent of the present invention can act as a water-and oil-repellent and a stainproofing agent. DETAILED DESCRIPTION OF THE INVENTION The graft fluorocopolymer according to the present invention has an average molecular weight of usually from 5,000 to 1,000,000, preferably from 10,000 to 20,000. Specific examples of the fluoromonomer used for the preparation of the graft fluorocopolymer are the following monomers, a typical example of which is a (meth)acrylate containing a polyfluoroalkyl group: R f -(CH 2 ) n OCOCR 3 =CH 2 R f -COO(CH 2 ) n CR 3 =CH 2 R f -O-Ar-CH 2 OCOCR 3 =CH 2 wherein R f is a polyfluoroalkyl group or polyfluoroalkenyl group having 3 to 21 carbon atoms, R 1 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R 2 is an alkylene group having 1 to 10 carbon atoms, R 3 is a hydrogen atom or a methyl group, Ar is an arylene group which may have a substituent group, and n is an integer of 1 to 10. Specific examples of the fluoromonomer are as follows: CF 3 (CF 2 ) 7 (CH 2 )OCOCH=CH 2 , CF 3 (CF 2 ) 6 (CH 2 )OCOC(CH 3 )=CH 2 , (CF 3 ) 2 CF(CF 2 ) 6 (CH 2 ) 2 OCOCH=CH 2 , CF 3 (CF 2 ) 7 (CH 2 ) 2 OCOC(CH 3 )=CH 2 , CF 3 (CF 2 ) 7 (CH 2 ) 2 OCOCH=CH 2 , CF 3 (CF 2 ) 7 SO 2 N(CH 3 )(CH 2 ) 2 OCOCH=CH 2 , CF 3 (CF 2 ) 7 SO 2 N(C 2 H 5 )(CH 2 ) 2 OCOC(CH 3 )=CH 2 , (CF 3 ) 2 CF(CF 2 ) 6 CH 2 CH(OCOCH 3 )CH 2 OCOC(CH 3 )=CH 2 , (CF 3 ) 2 CF(CF 2 ) 8 CH 2 CH(OH)CH 2 OCOCH=CH 2 , CF 3 C 6 F 10 (CF 2 ) 2 SO 2 N(CH 3 )(CH 2 ) 2 OCOCCH=CH 2 , The macromonomer which is copolymerized with the fluoromonomer is of the formula: In the formula (I), X is a hydrogen atom or methyl group, A is COOR (wherein R is a linear or branched alkyl group having 1 to 22 carbon atoms), CN or a phenyl group, n is from 10 to 500, Z is a (meth)acryloyloxy group, a styryl group, an allyl group, or a vinyl ester group, and D is -S-CH 2 CH 2 - or -CH 2 CH 2 OCO- Specific non-limiting examples of the macromonomer are macromonomers having a (meth)acrylate repeating unit such as wherein m is 10 to 500 and n is 1 to 22, for example, wherein m is 10 to 500, wherein m is 10 to 500, wherein m is 10 to 500; or wherein m is 10 to 500, wherein m is 10 to 500, and macromonomers having a styrene repeating unit such as wherein m is 10 to 500. When the textile treatment agent is used for carpets, the use of fluorine-free macromonomers having a glass transition temperature or melting point of at least 35°C gives an improved dry-soil stainproof property. Typical methods for preparing the macromonomer having an alkyl (meth)acrylate repeating unit are a method comprising radically polymerizing alkyl (meth)acrylate in the presence of a mercaptan chain transfer agent having a carboxyl group to give a polymer having a carboxyl group at one molecular end and then reacting the polymer with a (meth)acrylate having an epoxy group; or a method comprising radically polymerizing alkyl (meth)acrylate in the presence of a mercaptan chain transfer agent having a hydroxyl group such as 2-mercaptoethanol to give a polymer having a hydroxyl group at one molecular end and then reacting the polymer with (meth)acrylic acid halide or then conducting a reaction with a diisocyanate followed by a reaction with 2-hydroxyethyl methacrylate. The fluorine-free alkyl (meth)acrylate macromonomer used in the present invention may be any commercially available one, for example, the macromonomers manufactured by Toagosei Chemical Industry Ltd., Co. having a methyl methacrylate repeating unit, e.g. AA-6 (number average molecular weight Mn: 6,000) and AA-2 (Mn: 2,000), having a butyl acrylate repeating unit, e.g. AB-6 (Mn: 6,000) or having a stearyl methacrylate repeating unit, e.g. MM8-SMA (Mn: 9,000). In order to give the fiber softness, the alcohol moiety of the above alkyl (meth)acrylate polymeric portion preferably has 12 to 22 carbon atoms. The number of repeating units in the polymeric portion of the macromonomer is from 10 to 500. The graft copolymer used in the present invention contains at least 30 % by weight of the fluoromonomer as a constituent unit. If the amount is smaller than 30 % by weight, the excellent water- and oil-repellency and stainproof property cannot be obtained. The amount of the used fluorine-free macromonomer is from 1 to 70 % by weight. If the amount is smaller than 1 % by weight, the water- and oil-repellency, the stainproof property and the softness cannot be improved. If the amount is larger than 70 % by weight, no decreases of water-repellency, stainproof property and softness are observed but the oil-repellency disadvantageously decreases. In the present invention, another fluorine-free copolymerizable monomer can be added in an amount of no more than 69 % by weight of the copolymer in addition to the above monomers. Specific examples of the other fluorine-free monomer are ethylene, vinyl acetate, vinyl chloride, vinylidene halide, (meth)acrylic acid, (meth)acrylonitrile, styrene, α-methylstyrene, (meth)acrylamide, N-methylol(meth)acrylamide, alkyl (meth)acrylate, hydroxymethyl (meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, 3-chloro-2-hydroxypropyl (meth)acrylate, polyethyleneglycol (meth)acrylate, polypropyleneglycol (meth)acrylate, methoxypolyethyleneglycol (meth)acrylate, methoxypolypropyleneglycol (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, vinyl alkyl ether, butadiene, isoprene, chloroprene, glycidyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, maleic anhydride, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, dicyclopentenyl (meth)acrylate, methacrylic acid hydroxypropyltrimethylammonium chloride and methacrylic acid ethyltrimethylammonium chloride. The copolymerization with these monomers may improve various properties such as water- and oil-repellency, the stainproof properties such as the dry soil stainproof property, dye attachment prohibition and soil releasability, the anti-static property, the antibacterial property, friction resistance, cleaning resistance, feeling, and dispersion stability in a medium such as water. The graft copolymer of the present invention can be prepared by any usual polymerization method, such as solution polymerization, suspension polymerization, emulsion polymerization and bulk polymerization. For example, in the solution polymerization, the fluoromonomer and the fluorine-free macromonomer are dissolved in an organic solvent in the presence of a polymerization initiator, the atmosphere is replaced with nitrogen, and the mixture is heated at 50-120°C for several hours with stirring. Specific examples of the polymerization initiator are azobisisobutyronitrile, benzoyl peroxide, di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide, tert-butyl peroxypivalate and diisopropyl peroxydicarbonate. The amount of polymerization initiator is preferably from 0.01 to 5 parts by weight per 100 parts by weight of the monomer. The organic solvent is inactive to and dissolves the fluoromonomer and the fluorine-free macromonomer. Specific examples of the organic solvent are pentane, hexane, heptane, octane, cyclohexane, benzene, toluene, xylene, petroleum ether, tetrahydrofuran, 1,4- dioxane, methyl ethyl ketone, methyl isobutyl ketone, ethyl acetate, butyl acetate, 1,1,2,2-tetrachloroethane, 1,1,1-trichloroethane, trichloroethylene, perchloroethylene, tetrachlorodifluoroethane and trichlorotrifluoroethane. The amount of organic solvent is preferably from 50 to 1,000 parts by weight per 100 parts by weight of the monomer. For example, in the emulsion polymerization, the fluoromonomer and the fluorine-free macromonomer are emulsified in water, the atmosphere is replaced with nitrogen, and the mixture is heated at 50 to 80°C for several hours with stirring to conduct the copolymerization. Specific examples of a polymerization initiator are benzoyl peroxide, lauroyl peroxide, tert-butyl perbenzoate, 1-hydroxycyclohexylhydroperoxide, 3-carboxypropionyl peroxide, acetyl peroxide, azobisisobutylamidine-dihydrochloride salt, azobisisobutyronitrile, sodium peroxide, potassium persulfate, ammonium persulfate, di-tert-butyl peroxide, lauryl peroxide, cumene hydroperoxide, tert-butyl peroxypivalate and diisopropyl peroxydicarbonate. The amount of polymerization initiator is preferably from 0.01 to 5 parts by weight per 100 parts by weight of the monomer. In order to achieve a high graft efficiency and excellent shelf stability of an aqueous dispersion of the graft copolymer, it is preferable to use an emulsifying apparatus giving a high shear energy such as a high pressure homogenizer and an ultrasonic homogenizer so as to finely disperse the monomer in water and it is preferable to use an oil-soluble polymerization initiator. The emulsifier may be cationic, anionic or nonionic. The amount of emulsifier is preferably from 0.5 to 10 parts by weight per 100 parts by weight of the monomer. When the fluoromonomer is not completely compatible with the fluorine-free macromonomer, it is possible to add a water-soluble organic solvent or low-molecular-weight monomer which is compatible with both monomers so as to improve compatibility between the fluoromonomer and the fluorine-free macromonomer so that emulsification and copolymerization are facilitated. Specific examples of the water-soluble organic solvent used for this purpose are acetone, methyl ethyl ketone, ethyl acetate, dipropyleneglycol monomethyl ether, propylene glycol, dipropylene glycol, tripropylene glycol and ethanol. The amount of water-soluble organic solvent is preferably from 10 to 40 parts by weight per 100 parts by weight of water. Specific examples of the low-molecular-weight monomer are methyl methacrylate, glycidyl methacrylate and 2,2,2-trifluoroethyl methacrylate. The amount of low-molecular-weight monomer is preferably from 5 to 95 parts by weight per 100 parts by weight of the total amount of the fluoromonomer and the fluorine-free macromonomer. The material to be treated with the textile treatment agent of the present invention is not limited. Specific examples of the treated material are natural fibers such as cotton, hemp, wool and silk; semisynthetic fibers such as rayon and acetate; synthetic fibers such as polyamide, polyester, acryl, polypropylene, polyvinyl chloride and polyvinyl alcohol. The treated textile may be in any form of a fiber, a yarn or a fabric (for example, woven fabric and knitted fabric). The textile treatment agent of the present invention can be applied by any conventional procedure. For example, a solution or dispersion of the textile treatment agent in an organic solvent or water is adhered to the treated material by dip coating, spray coating or bubble coating and then the treated material is dried. If necessary, a suitable crosslinking agent is used together with the textile treatment agent to conduct the curing. In the treatment liquid, for example, in the case of dip coating, the concentration of the graft fluorocopolymer is from 0.1 to 10 % by weight. In addition to the textile treatment agent of the present invention, another stainproof agent, water-repellent or oil-repellent, an antibacterial agent, an antistatic agent, a flame retardant, an insecticide, a feeling controlling agent, a dye fixing agent and the like may be added. PREFERRED EMBODIMENT OF THE INVENTION The present invention will be illustrated by the following Preparative Examples and Examples which do not limit the present invention. Preparative Example 1 (Preparation by solution polymerization of a graft copolymer having a branch component of polymethyl methacrylate) In a 200 ml four-necked flask equipped with a reflux condenser, a nitrogen introducing tube, a thermometer and a stirrer, 10 g of a polymethyl methacrylate/methacryloyl group type macromonomer (AA-6 manufactured by Toagosei Chemical Industry Co. Ltd., number average molecular weight: 6,000, a macromonomer wherein the repeating unit is methyl methacrylate and the polymerizable end is a methacryloyl group, hereinafter referred to as "MMA-MM") and 10 g of CF 3 CF 2 (CF 2 CF 2 ) n (CH 2 ) 2 OCOCH=CH 2 (a mixture of compounds in which n is 3, 4 and 5 in a molar ratio of 6:3:1, hereinafter referred to as "FA") and 180 g of 1,1,1-trichloroethane were charged and heated to 60°C. Then, the atmosphere in the flask was replaced with nitrogen for 30 minutes. One gram of tert-butyl peroxypivalate (trade name: Perbutyl PV, manufactured by Nippon Oil & Fat Co. Ltd.) was added and the polymerization was conducted for 6 hours. Gas chromatography analysis revealed that at least 99 % of the monomer was consumed. Disappearance of the elution peak of the macromonomer in GPC confirmed the complete polymerization of the macromonomer. Preparative Example 2 (Preparation by solution polymerization of a graft copolymer having a branch component of polystearyl methacrylate) In a 200 ml four-necked flask, 10 g of a polystearyl methacrylate/methacryloyl group type macromonomer (MM8-SMA, manufactured by Toagosei Chemical Industry Co. Ltd.; number average molecular weight: 9,000; used after removing toluene from the commercially available 50 wt % solution in toluene; a macromonomer in which the repeating unit is stearyl methacrylate and the polymerizable molecular end is a methacryloyl group; hereinafter referred to as "SMA-MM"), 10 g of FA and 180 g of 1,1,1-trichloroethane were charged and heated to 60°C. Then, the atmosphere in the flask was replaced with a nitrogen gas for 30 minutes. One gram of Perbutyl PV was added and the polymerization was conducted for 6 hours. Gas chromatography analysis revealed that at least 99 % of the monomer was consumed. Disappearance of the elution peak of the macromonomer in GPC confirmed the complete polymerization of the macromonomer. Preparative Example 3 (Preparation by emulsion polymerization of a graft copolymer having a branch component of polymethyl methacrylate) A mixture consisting of 50 g of MMA-MM, 50 g of FA, 135 g of deionized water, 40 g of acetone, 0.1 g of n-lauryl mercaptan, 1 g of stearyltrimethylammonium chloride and 2 g of polyoxyethyleneoctylphenylether was heated to 60°C and emulsified by the use of a high pressure homogenizer. The resultant emulsion was charged in a 300 ml four-necked flask equipped with a reflux condenser, a nitrogen introducing tube, a thermometer and a stirrer and kept at 60°C in the nitrogen atmosphere for one hour with intimate stirring. Then, a solution of 1 g of azobisisobutyronitrile (AIBN) in 5 g of acetone was added to initiate polymerization and the mixture was heated at 60°C for 3 hours with stirring. Gas chromatography analysis revealed that at least 99 % of the monomer was consumed to prepare the resultant graft copolymer. Disappearance of the elution peak of the macromonomer in GPC confirmed the complete polymerization of the macromonomer. Preparative Example 4 (Preparation by emulsion polymerization of a graft copolymer having a branch component of polystearyl methacrylate) A mixture consisting of 50 g of SMA-MM, 50 g of FA, 135 g of deionized water, 40 g of acetone, 0.1 g of n-lauryl mercaptan, 1 g of stearyltrimethylammonium chloride and 2 g of polyoxyethyleneoctylphenylether was heated to 60°C and emulsified by the use of a high pressure homogenizer. The resultant emulsion was charged in a 300 ml four-necked flask equipped with a reflux condenser, a nitrogen introducing tube, a thermometer, a stirrer and kept at 60°C in nitrogen for one hour with intimate stirring. Then, a solution of 1 g of azobisisobutyronitrile (AIBN) in 5 g of acetone was added to initiate polymerization and the mixture was heated at 60°C for 3 hours with stirring. Gas chromatography analysis revealed that at least 99 % of the monomer was consumed. Disappearance of the elution peak of the macromonomer in GPC confirmed the complete polymerization of the macromonomer. Comparative Preparative Example 1 (Preparation by solution polymerization of a random copolymer) In a 200 ml four-necked flask, 10 g of stearyl methacrylate (SMA), 10 g of FA and 180 g of 1,1,1-trichloroethane were charged. The mixture was heated at 60°C, and the atmosphere in the flask was replaced with nitrogen for 30 minutes. One gram of Perbutyl PV was added to initiate polymerization and the polymerization was conducted for 6 hours. Gas chromatography analysis revealed that at least 99 % of the monomer was consumed. Comparative Preparative Example 2 (Preparation by solution polymerization of a graft copolymer having a branch component of polyfluoroacrylate) A copolymer was prepared according to the method for preparing a graft copolymer described in Japanese Patent Kokai Publication No. 73712/1986. 10 g of SMA and 180 g of toluene were charged in a 200 ml four-necked flask and heated at 80°C. The atmosphere in the flask was replaced with nitrogen for 30 minutes. Benzoyl peroxide (BPO) was added and the polymerization was conducted for 6 hours. Gas chromatography analysis revealed that at least 99 % of the monomer was consumed in the resultant polymer. 10 g of FA and 0.1 g of BPO were added to the toluene solution containing the polymer and the mixture was heated to 80°C. The graft polymerization was conducted under nitrogen atmosphere for 6 hours with stirring. Gas chromatography analysis revealed that at least 99 % of the monomer was consumed to prepare the resultant graft copolymer. Since the undissolved part of the resultant graft copolymer in fluorinated hydrocarbon R-113 was 5 g, the graft efficiency was assumed to be 50 %. Comparative Preparative Example 3 (Preparation by solution polymerization of a random copolymer) The same procedure as in Preparative Example 1 was repeated to prepare a random copolymer, except that methyl methacrylate was used instead of MMA-MM. Preparative Example 5 (Preparation by emulsion polymerization of a graft copolymer having a branch component of polymethyl methacrylate) A mixture consisting of 50 g of FA, 10 g of MMA-MM, 40 g of methyl methacrylate, 300 g of deionized water, 5 g of polyoxyethyleneoctylphenylether, 5 g of stearyltrimethylammonium chloride and 0.1 g of n-lauryl mercaptan was heated to 60°C and emulsified by the use of a high pressure homogenizer. The resultant emulsion was charged in a 500 ml four-necked flask equipped with a reflux condenser, a nitrogen introducing tube, a thermometer and a stirrer and the atmosphere was replaced with nitrogen for 30 minutes. Then, a solution of 0.5 g of azobisisobutyronitrile in 5 g of ethyl acetate was added and the polymerization was conducted at 60°C for 3 hours. Gas chromatography analysis and GPC analysis revealed that at least 99 % of the monomer was consumed and the graft copolymer was obtained. Preparative Example 6 (Preparation by emulsion polymerization of a graft copolymer having a branch component of polystyrene) The same procedure as in Preparative Example 5 was repeated to prepare the graft copolymer, except that a polystyrene/methacryloyl group type macromonomer (AS-6, manufactured by Toagosei Chemical Industry Co. Ltd.; number average molecular weight: 6,000; a macromonomer in which the repeating unit is styrene and the polymerizable end is a methacryloyl group; hereinafter referred to as "St-MM") and styrene were used instead of MMA-MM and methyl methacrylate, respectively. Preparative Example 7 (Preparation by emulsion polymerization of a graft copolymer having a branch component of polymethyl methacrylate) The same polymerization as in Preparative Example 5 was repeated to prepare the graft copolymer, except that 50 g of FA, 25 g of MMA-MM, 25 g of methyl methacrylate, 250 g of deionized water, 50 g of ethyl acetate, 5 g of polyoxyethyleneoctylphenylether, 5 g of stearyltrimethylammonium chloride and 0.1 g of n-lauryl mercaptan were used as the raw materials. Comparative Preparative Example 4 (Preparation by emulsion polymerization of a random copolymer) The same polymerization was conducted as in Preparative Example 5 to prepare the random copolymer, except that MMA-MM was not used and the amount of methyl methacrylate was increased by the amount of MMA-MM. Comparative Preparative Example 5 (Preparation of a mixture of homopolymers) As in Preparative Example 5, only FA was used as the monomer to conduct the emulsion polymerization so as to give a fluorohomopolymer and, separately, only methyl methacrylate was used as the monomer to conduct the emulsion polymerization so as to give a methyl methacrylate homopolymer. Both of the resultant homopolymers were mixed in the solid ratio of 50:50 to prepare a treatment liquid having a solid content of 3 % by weight. Comparative Preparative Example 6 (Preparation by emulsion polymerization of a random copolymer) The same polymerization was conducted as in Preparative Example 6 to prepare the random copolymer, except that St-MM was not used and the amount of styrene was increased by the amount of St-MM. Preparative Example 8 (Preparation by emulsion polymerization of a graft copolymer having a branch component of polybutyl acrylate) The same procedure as in Preparative Example 5 was repeated to prepare the graft copolymer, except that 70 g of FA, 25 g of a polybutyl acrylate/methacryloyl group type macromonomer (AB-6, manufactured by Toagosei Chemical Industry Co. Ltd.; number average molecular weight: 6,000; a macromonomer in which the repeating unit is butyl acrylate and the polymerizable end is a methacryloyl group; hereinafter referred to as "BuA-MM"), 5 g of butyl acrylate, 300 g of deionized water, 5 g of polyoxyethyleneoctylphenylether, 5 g of stearyltrimethylammonium chloride and 0.1 g of n-lauryl mercaptan were used as the raw materials. Comparative Preparative Example 7 (Preparation by emulsion polymerization of a random copolymer) The same polymerization was conducted as in Preparative Example 8 to prepare the random copolymer, except that BuA-MM was not used and the amount of butyl acrylate was increased by the same amount of BuA-MM. Examples 1 and 2 and Comparative Examples 1 and 2 The copolymer prepared in each of Preparative Examples 1 and 2 and Comparative Preparative Examples 1 and 2 was diluted with n-decane to prepare a resinous liquid having a solid content of 0.5 % by weight. A mixed broad fabric of polyester and cotton (65 % of polyester and 35 % of cotton) was immersed in the resinous liquid, squeezed with a mangle, dried in air and dried at 100°C for 3 minutes. The water- and oil-repellency, the dry cleaning SR property and the softness of the treated fabric and the low-temperature stability of the product were tested (Table 1). Examples 3 and 4 The graft copolymer prepared in each of Preparative Examples 3 and 4 was diluted with water to prepare a resinous liquid having a solid content of 0.5 % by weight. A mixed broad fabric of polyester and cotton (65 % of polyester and 35 % of cotton) was immersed in the resinous liquid, squeezed with a mangle, predried at 80°C for 3 minutes and thermally treated at 150°C for 3 minutes. The water- and oil-repellency, the dry cleaning SR property and the softness of the treated fabric were tested (Table 1). Example 5 and Comparative Example 3 The copolymer prepared in each of Preparative Example 1 and Comparative Preparative Example 3 was diluted with acetone to prepare a treatment liquid having a solid content of 1 % by weight. A nylon loop piled carpet cloth (not backing-treated) was immersed in the treatment liquid, squeezed, dried in air and dried at 130°C for 3 minutes. The water- and oil-repellency and the dry soil stainproof property of the treated carpet were tested (Table 2). Examples 6-9 and Comparative Examples 4-7 The copolymer prepared in each of Preparative Examples 5, 6, 7 and 8 and Comparative Preparative Examples 4, 6 and 7 was diluted with water to prepare a treatment liquid having a solid content of 3 % by weight. The treatment liquid was sprayed on a nylon loop piled carpet cloth (not backing-treated) at a coating amount of 100 g/m 2 and the carpet was thermally treated at 130°C for 5 minutes. The water- and oil-repellency and the dry soil stainproof property of the treated carpet were tested (Table 2). A treatment liquid containing the mixture of homopolymers prepared in Comparative Preparative Example 5 was used to treat the carpet and the test was conducted. EVALUATIONS OF PROPERTIES 1. Water repellency The test was conducted as follows: (1) Method A The water repellency is expressed by the water repellency No. determined by the spray method according to JIS-L-1092. Water repellency No. State 100 No wet on the surface 90 Slight wet on the surface 80 Partial wet on the surface 70 Wet on the surface 50 Wet over the whole surface 0 Complete wet on the front and back surfaces (2) Method B Droplets of an isopropyl alcohol/water mixture having the following composition are positioned on the carpet cloth. The maximum content of isopropyl alcohol in the liquid keeping the shape of the droplet after 3 minutes is expressed as the water repellency. Composition of mixture (% by volume) Isopropyl alcohol Water 50 50 40 60 30 70 20 80 10 90 0 100 2. Oil repellency The oil repellency is determined by, according to AATCC-TM-118-1966, dropping several drops (diameter: about 4 mm) of the following test solution on two positions of a surface of a test cloth, observing the penetration state of the drops after 30 seconds, and the maximum value of oil repellency of the test solution having no penetration is expressed as the oil repellency. Oil repellency Test solution Surface tension (dyne/cm, 25°C) 8 n-Heptane 20.0 7 n-Octane 21.8 6 n-Decane 23.5 5 n-Dodecane 25.0 4 n-Tetradecane 26.7 3 n-Hexadecane 27.3 2 n-Hexadecane/Nujol (35/65 by weight) 29.6 1 Nujol 31.2 0 Inferior to 1 - The wash resistance is determined by conducting three times the steps of washing the fabric for 15 minutes, rinsing the fabric for 10 minutes and drying the fabric under the use of a washing liquid consisting of 40 g of a detergent (tradename: Zab) and 20 L of water and a temperature of 40°C in a household electrical washing machine, and then measuring the water repellency and the oil repellency. 3. Stainproof property (1) Dry cleaning SR test The test for determining the soil release property at dry cleaning (dry cleaning SR property) is conducted as follows. A test cloth is spread on a piece of blotting paper horizontally spread and then five drops of a dirty motor oil (SAE20W-40, drained after the feed into an engine of a compact car and running for 4,000 km) are dropped on the test cloth. A polyethylene sheet is positioned on the test cloth and a weight of 2 kg is positioned on the polyethylene sheet. After 60 seconds, the weight and the polyethylene sheet are removed. Any excess oil is wiped off and the test cloth is kept standing at room temperature for 24 hours. The test cloth and a ballast cloth together having a total weight of 450 g are charged into a dry cleaning tester, dry cleaning is conducted at room temperature for 5 minutes using 3.78 L of perchloroethylene, and the test cloth is air-dried. The state of the remaining stain of the dried test cloth is compared with a standard photograph plate so that the state of the remaining stain is expressed by the corresponding determined grade shown below. The standard photograph plate is one according to AATCC Test Method 130-1970. Determined grade Criteria 1.0 Stain remarkably remains 2.0 Stain considerably remains 3.0 Stain slightly remains 4.0 Stain is not noticeable 5.0 Stain does not remain (2) Dry soil stainproof property Firstly, according to JIS L 1023-1992, a carpet is contaminated with a dry soil having the following composition. Components Weight ratio % Peat moss 40 Portland cement (JIS R 5210) 17 Kaolin clay (JIS K 8746) 17 Diatomaceous earth (JIS K 8330) 17 Carbon black (JIS K 5107) 0.1 Ferric (III) oxide for ferrite (JIS K 1462) 0.15 Nujol 8.75 After residual soil on the sample is removed by the use of an electrical vacuum cleaner, brightness of the sample surface is measured by a colorimeter and a contamination ratio is calculated according to the following equation to evaluate the stainproof property against dry soil. Contamination ratio (%) = [(L 0 - L)/L 0 ] x 100 wherein L 0 is the brightness of the sample before contamination, and L is the brightness of the sample after contamination. 4. Softness A sensual evaluation is made by technical panelists. 5. Stability at low temperature The copolymer prepared in each of Preparative Examples 1 and 2 and Comparative Preparative Examples 1 and 2 is diluted with n-decane to prepare a resinous liquid having a solid content of 5 % by weight. After the resinous liquid is kept in a constant temperature bath at -5°C for one day, the coagulation state is visually evaluated. No coagulation is expressed by O, and coagulation is expressed by X. The test results conducted for the polyester/cotton mixed broad fabric (Examples 1 to 4 and Comparative Examples 1 and 2) are shown in Table 1. Polymer Type of polymer Polymerization Method Branch of graft copolymer Water-repellency / Oil-repellency Dry cleaning SR property Soft-ness Stability at low temperature Initial Washing three times Ex. 1 Preparative Example 1 Graft Solution polymerization Methyl methacrylate 100+/6 80/3 4 Hard O Ex. 2 Preparative Example 2 Graft Solution Polymerization Stearyl methacrylate 100+/6 80+/3 5 Soft O Ex. 3 Preparative Example 3 Graft Emulsion polymerization Methyl methacrylate 100+/6 80/3 4 Hard - Ex. 4 Preparative Example 4 Graft Emulsion polymerization Stearyl methacrylate 100+/6 80+/3 5 Soft - Com. Ex. 1 Comparative Preparative Example 1 Random Solution polymerization - 90/4 50/1 1 Some what soft X Com. Ex. 2 Comparative Preparative Example 2 Graft Solution polymerization FA 80/4 50/1 1 Hard X As becomes clear from the results of Table 1, a graft copolymer having a backbone of fluoromonomer used in the present invention gives better water- and oil-repellency, washing resistance and dry cleaning SR property than a graft copolymer having a branch of fluoromonomer or a random copolymer having the same monomer composition. In addition, stability at low temperature is improved. The results for carpets (Examples 5 to 9 and Comparative Examples 3 to 7) are shown in Table 2. Polymer Type of polymer Polymerization Method Repeating unit derived from fluorine-free monomer Water repellency Oil repellency Dry soil stainproof property (Contamination ratio) Ex. 5 Preparative Example 1 Graft Solution polymerization Methyl methacrylate 50 6 20 Com. Ex. 3 Comparative Preparative Example 3 Random Solution polymerization Methyl methacrylate 40 2 28 Ex. 6 Preparative Example 5 Graft Emulsion polymerization Methyl methacrylate 30 4 26 Ex. 7 Preparative Example 6 Graft Emulsion polymerization Styrene 30 4 28 Ex. 8 Preparative Example 7 Graft Emulsion polymerization Methyl methacrylate 40 5 22 Com. Ex. 4 Comparative Preparative Example 4 Random Emulsion polymerization Methyl methacrylate 20 2 35 Com. Ex. 5 Comparative Preparative Example 5 Mixture of homopolymers Emulsion polymerization Methyl methacrylate 10 1 28 Com. Ex. 6 Comparative Preparative Example 6 Random Emulsion polymerization Styrene 20 2 38 Ex. 9 Preparative Example 8 Graft Emulsion polymerization Butyl acrylate 40 5 32 Com. Ex. 7 Comparative Preparative Example 7 Random Emulsion polymerization Butyl acrylate 20 3 40 As becomes clear from the results of Table 2, the graft copolymer used in the present invention gives better water- and oil-repellency and stainproof property than a random copolymer and a mixture of homopolymers having the same monomer composition. EFFECT OF THE INVENTION As explained above, the graft copolymer according to the present invention has excellent effects as a water- and oil-repellent and as a stainproof agent.

Claims: A textile treatment agent which comprises, as an active component, a graft fluorocopolymer having a backbone of a polymer of a fluoromonomer and a branch of a polymer of a macromonomer, the graft fluorocopolymer being obtainable by copolymerizing the fluoromonomer with the macromonomer which is a fluorine-free macromonomer having a terminal addition-polymerizable unsaturated group copolymerizable with the fluoromonomer, wherein the fluorine-free macromonomer is of the formula: wherein X is a hydrogen atom or methyl group, A is COOR (wherein R is a linear or branched alkyl group having 1 to 22 carbon atoms), CN or a phenyl group, n is from 10 to 500, Z is a (meth)acryloyloxy group, a styryl group, an allyl group, or a vinyl ester group, and D is -S-CH 2 CH 2 - or -CH 2 CH 2 - and the amount of units derived from the fluoromonomer in the graft copolymer is at least 30% by weight and the amount of units derived from the fluorine-free macromonomer is from 1 to 70% by weight. The textile treatment agent according to claim 1, wherein the fluorine-free macromonomer has a glass transition temperature or melting point of at least 35°C.

Inventors: ENOMOTO TAKASHI, HAYASHI KAZUNORI, KUBO MOTONOBU, MORITA MASAMICHI, SANO TARO, UEDA AKIHIKO, ENOMOTO, TAKASHI, HAYASHI, KAZUNORI, KUBO, MOTONOBU, MORITA, MASAMICHI, SANO, TARO, UEDA, AKIHIKO, ENOMOTO, TAKASHI, YODOGAWA WORKS OF DAIKIN IND LTD, HAYASHI, KAZUNORI YODOGAWA WORKS OF DAIKIN IND LTD, KUBO, MOTONOBU, YODOGAWA WORKS OF DAIKIN IND. LTD., MORITA, MASAMICHI YODOGAWA WORKS OF DAIKIN IND LTD, SANO, TARO YODOGAWA WORKS OF DAIKIN INDUSTRIES LTD, UEDA, AKIHIKO, YODOGAWA WORKS OF DAIKIN IND. LTD.
Applicants: DAIKIN IND LTD, DAIKIN INDUSTRIES, LIMITED
Application year: 1994
Main classification: D06M15
IPC codes: C09K3, C08F290, D06M15, C08F299